Functionally-substituted ethylmercaptocyclohexanones



United States Patent 3,409,664 F UN C'I'IONALLY-SUBSTITUTED ETHYL- MERCAPTOCYCLOHEXANONES Sheldon Chibuik, Plaiufield, Harold M. Foster, Middlesex, Harold A. Kaufman, New Brunswick, and Laverne A. Click, Edison, N.J., assignors to Mobil Oil Corporation, a corporation of New York No Drawing. Filed Dec. 20, 1965, Ser. No. 515,252

Claims. (Cl. 260-488) This invention relates to mercaptocyclohexanones. It is more particularly concerned with a novel class of substituted 3-ethylmercaptocyclohexanones.

The compounds of this invention are 3-ethylmercaptocyclohexanones having certain functional groups in the 2- position of the ethylmercapto group, as more fully described hereinafter. These substituted cyclohexanones are No. 458,771, filed May 25, 1965; and Ser. No. 468,094, filed June 29, 1965.

Accordingly, it is a broad object of this invention to provide a novel class of substituted cyclohexanones. Another object is to provide novel substituted ethylmcrcaptocyclohexanones. A specific object is to provide novel lowing detailed description.

In general, this invention provides compounds having the formula:

1 ll 6 H RI,"

5 3 Siam" wherein R is an alkyl (C -C alkenyl (C -C alkoxy (C -C alkylthio (C -C di(C C )alkylamin0, or cyano; n is 0 to 3; R is H, alkyl (C -C alkenyl (C -C alkoxy (C -C halogen, or alkylthio (C -C R, R, and R"" are H, hydroxyl, alkoxy (C -C mercapto, alkylthio (C -C halogen, amino, alkylamino (C -C dialkylamino (C -C or acetoxy; or R and R"" together are a bivalent group selected from =0,

OCHCHO, OCHCHCHO, -SCHCHO, -SCHCHS X X 1'; I i 2 i 1'; 1'; I i

SCHCHOH0, and -SCHCHCHS i i i X in which X is H, alkyl (C C or alkenyl (C C 3,409,664 Patented Nov. 5, 1968 Compounds of this invention that are particularly useful as intermediates for preparing 4-hydroxybenzothiophene are those having the formula:

this invention can be employed. For example, as is illustrated hereinafter, a Z-mercaptoethyl derivative having a functional group of groups on the 1-position, such as Z-mercaptoethyl acetate, can be reacted with 2-cyclohexen-l-one, by adding the mercapto group across the double bond. Generally, such addition is effected at temperatures ranging from ambient temperatures up to about C., with or without the use of catalysts.

Another method for the synthesis of the compounds of this invention, involves the reaction between 3-mercaptocyclohexanone and an olefinic compound containing the functional group or groups. The 3-mercaptocyclohexanone is readily prepared by the addition of hydrogen sulfide across the double bond of 2-cyclohexen-1-one. This method of synthesis is illustrated in the following typical equations:

0 H /OR CH2=C S 0R SCH2OH(OR)2 CH=CHOCOOH3 H SCHCH2OCOCH:

SH H

oH,=cHoR SCHzCHzOR CH=C C12 w SCH CHClz Non-limiting examples of typical compounds of this invention are 3- 2,Z-diethoxyethylmercapto) cyclohexanone;

3- 2,2-dimethoxyethylmercapto) -5-ethylcyclohexanone;

3-(2,2dioctoxyethylmercapto) cyclohexanonc;

3 -(2-acetoxyethylmercapto) -4-hexenylcyclohexanone;

3 2-bromoethylmerc apto) cyclohexanone 3-( 2-chloroethylmcrcapto) cyclohexanone;

3 2-acetoxyethylmercapto) cyclohexanone;

3- (2,2-dimethoxyethylmercapto) -4-methylcyclohexanone;

3-(2-ethoxyethylmercapto) cyclohexanone;

3 2,2-dichloroethylmerc apto) cyclohexanone;

3 2,2-dimethoxyethylrnercapto) cyclohexanone; 3 (2,2-dimethoxyethyl) -5 -octylcyclohexanone, and 3- (2,2-dimethoxyethyl) -6-propenylcyclohexanone.

In many instances, the compounds to be disclosed in this invention were recognized and/or first identified by V.P.C. (Vapor Phase Chromatographic) analysis. In several instances pure samples were obtained by condensing the effluent from a V.P.C. column. The retention time of these compounds by V.P.C. analysis is an important, and sometimes only, physical property available for characterization. The following description of conditions and parameters will serve to form the basis for a description of the physical property V.P.C. retention time on a new column designated Column A.

60 mls. per min. 40

Based on the foregoing, some typical V.P.C. retention times" for Column A are as follows:

Sample Column A Compound Size, (from injection) pl. V.P.C. Retention Time, minutes 2-cyclohexen-1one 1 3 5-3.7 Dimethyl mereaptoacetal.. 1 1. 5-1. 7 Diethyl mercaptoacetaL--- 1 2. 2-2. 4 2-mereaptoethyl acetate 1 2. 6-2. 8

In well-conditioned All conditions and parameters are otherwise as described a similar manner, some work V.P.C. column,

was done using an old designated Column B.

hereinabove. Some typical V.P.C. retention times for Column B are as follows:

Sample Column B Compound Size, V .P.C. Retention pl. Time, minutes 2-cyclohexen-1-one 1 2. 1-2. 3 2-mercaptoethyl 2 1. 51-1. 7 Z-mercaptoethyl chloride. 2 0. 7-0. 9

Example 1 To a mixture of diethyl mercaptoacetal (ten drops) and 2-cyclohexen-1-one (ten drops) was added two drops of piperidine. The reaction mixture was shaken to provide good mixing. It was noted that an exothermic reaction had occured. After one-half hour, approximately of the adduct had formed. Results of V.P.C. analysis (2 pl. sample of reaction mixture) was as follows:

Column A, V.P.C. Retention Compound: Time, minutes Diethyl mercaptoacetal 2.5

2-cyclohexen-1-one 3.6 Adduct, 3-(2,2-diethoxyethylmercapto) cyclohexanone 14.65

In a larger scale run, the boiling point of the adduct was 123-125 C./0.9 mm. n 1.4872; this latter sample was 95% pure (V.P.C. analysis).

A sample obtained by condensing the efiluent from a V.P.C. column had infrared and nuclear magnetic reso-- nance spectra consistent with the proposed structure.

' at 5060 C. during stirring.

Example 2 To a mixture of 2-cyclohexen-l-one (22.7 g.) and dimethyl mercaptoacetal (28.9 g.) was added piperidine (0.5 g.). A violent exotherm was noted; the temperature rose to 95 C. within one to two minutes. After standing at room temperature, during stirring, for about a day, approximately 50% of the adduct had formed. Results of V.P.C. analysis (1 ,ul. sample of reaction mixture) are as follows:

1 Column A, V.P.C. Retention Compound: Time, minutes Dimethyl mercaptoacetal l. 2-cyclohexen-1 one 3.5 Adduct, 3-(2,2-dimethoxyethylmercapto) cyclohexanone 14.25 A sample obtained by condensing the efiluent from a V.P.C. column had infrared and nuclear magnetic resonance spectra consistent with the proposed structure.

Example 3 A mixture of 2-cyclohexen-l-one (41.4 g.) 2-mercaptoethyl acetate (64 g.) and acetic acid (5. g.) was heated at C. during stirring for two days. An additional 50 ml. of acetic acid was added and heating was continued for four more hours. After removal of the acetic acid, the residual oil was distilled under reduced pressure. One of the fractions, BJP. ll2ll5 C./0.l8 mm., 11 1.5056, contained Adduct in addition to both starting materials. V.P.C. analysis (2 #1. sample) gave the following results:

Column A, V.P.C. Retention Compound: Time, minutes Z-mercaptoethyl acetate 2. 2-cyclohexe'n-1-one 3.7 Adduct, 3-(Z-acetoxyethylmercapto) cyclohexanone 1 6.2

A pure sample was obtained by condensing the effiuent from a V.P.C. column.

Analysis.-Calcd. for C H O S: C, 55.52; H, 7.46. Found: C, 55.59, 55.61; H, 7.78, 7.73.

The infrared and nuclear magnetic resonance spectra of this sample were consistent with the proposed structure.

Example 4 A mixture of 2-cyclohexen-l-one (9.6 g.), Z-mercaptoethyl acetate (12 g.) and acetic acid (0.5 g.) was heated After one day, approximately 25% of the 'adduct had formed. Results of V.P.C. analysis (2 1. sample of reaction mixture) are as follows:

Column B,

V.P.C. Retention Compound: Time, minutes 2-mercaptoethyl acetate 1. 2-cyclohexen-1-one 2.2 Adduct, 3-(Z-acetoxyethylmercapto) cyclohexanone 14.0

Example 5 A mixture of 2-cyclohexen-1-one (35 g.), Z-mercaptoethyl chloride (40 g.) and acetic acid (2 g.) was stirred at room temperature for four days. At this time, approximately 30% of the adduct was present. Results of V.P.C.

analysis (2 pl. sample of reaction mixture) are as follows:

Column B,

V.P.C. Retention Compound: Time, minutes 2-mercaptoethyl chloride 0.7

2-cyclohexen-1-one 2.1 Adduct, 3-(2-chloroethylmercapto) cyclohexanone 12.5

In the foregoing examples, typical mercapto-substituted cyclohexanones of this invention have been illustrated and What is claimed is: 1. A compound having the formula:

group consisting of hydrois selected from the group wherein R and R References Cited UNITED STATES PATENTS.

3/1949 Kendall et a] OTHER REFERENCES Chem. Abstracts: 54; 3360 (1960); 56; 2344a (1962); 47; 8012c (1953).

LORRAINE A. WEINBERGER, Primary Examiner. V. GARNER, Assistant Examiner. 

1. A COMPOUND HAVING THE FORMULA: 